Bis (hexityl amino compounds) and functional derivatives thereof



United States PatentO g 1 a t i 2 e 1,4-dichlor-butene-2 1,10-dibrom-decane 7 2,302,821 p-XyIylene dichloride e BIS (HEXITYL AMINO COMPOUNDS) ANDFUNC- m-Xylylenc dibromide o v e TIONAL DERIVATIVES THEREOF v 't Dichlor-alkyl ethers and -polyalkylene ethers:

A i Dichlor-ethyl ether I a Zech fi l a g e 52 Bis bromo-ethyl ether of triethylene glycol Wtlli'm-ompany, mung on; e a corpora one a Dichloppmpyl ether 1; Hydroxy dichlor-aliphatic ethers:

No Drawing. Application March 16, 1953, 10 3,3-dichloro-2,2-dihydroxy dipropyl ether Serial No} 342,745 Chlor-aliphatic 1,2-epoxides: 1

Epichlorhydrin Chlor-ethyl ether of glyci'dol v I I 1 chloro-Z hydroxy-SA epoxy butane Thisinvention relates to organic c'hemical compounds, Diglycidyl ethers! 14 Claims. (Cl. 260-211) and more particularly to organic compounds containing i y i yl ether of y Qq two substituted hexityl amine radicals, and functional y' y fl IESOYCIHOI derivatives of such compounds. 7 e I Diglycidyl ether of 2.2-di(parahydroxy phenyl) It is an object of the invention to provide novel P p organic compounds containing two substituted heXityl Diglycidyl ether of ly amino radicals. Another object is to provide functional Diglycidyl ether of hy e glycol denvatlves of 2 hexltyl ammo compounds: Secondary heXityl amines coming within the scope of A further oblect 15 to Provlde novel Precesses t the hereinbefore-defined hexityl amine reactant f em paring bis glucamim COmPOunds and their functional ployed in the process and furnishing the hexityl amino derivatives. a p 1 v v radicalsofthe compounds of the invention include N The ebove a other obleets e m substituted glycamines, N-substituted fructamines and the parent 1n the course of the following description of the like, which compounds may bepl-epared b h dmlnventlon and In the appended elalmsgenation of hexoses in the presence of primary amines.

The t re cf'thc om c qn m t Specific hexityl amines which maybe employed in 36-: PreseIlt mventlon W111 be best understood m a cordance with the invention include N-methyl glucar'nine.

tion of processes for making them and an enumeration of N 1 f tami N ethy1 glucaminei N prop'yl the ee r h r enl to yleld the e fructamine, 'N-lauryl-, N-cetyl,, N-oleyland N-stearyl compoundse bls hexltyl ammo compounds of glucamines, N-ethanol fructamine, N-isopropanol glucn i are P p by causing two mo P amine, N-benzyl fructamine, N-phenyl glucamine, and tions of a secondary hexityl amine to're'act with one the 1 le e P PQ 'i n Ofa dif unct ional organic CQ As pointed out hereinbefore, the bis hexityl amine PQ such for f e as a dl'hahdet a dl'epexldet products of the invention are formed by the reaction of 2 l p y P l 1 p t molecular proportions of a secondary heXityl mine with Suitable dlfPncilonal g i comiwundswlth which one molecular proportion of a difunctional compound, secondary hexltyl am i c to f m the his hexityl all as defined and illustrated above. When the reacting amino products of the invention include the di-halides of functional group of the said defunctional compound is atomic num r g a t pr a ly ,w-dian epoxide group the reaction is one of addition and is halides, of aliphatic hydrocarbons and of araliphatic hyaccompanied by the generation of a hydroxyl group. drocarbons; glyceryl dichlorhydrin, symmetrical dichlor- Such a reaction is illustrated by the following equation alkyl ethers and -polyalkylene ethers; hydroxy dichlorshowing the reaction between butadienedioxide and aliphatic ethers; w-chlor-aliphatic 1,2 epoxides; butadiene methyl glucamine.

5" I ZCHlOH(CHOH)4CHzN-H Hz'C-- CHCfi-CH z $113 '7 7 CH! 0Ht0H(0HOH)toHr-NoHt0H(oH)'oii(0H)ol1tNoHt(0HOH)toH,ol1 dioxide and its homologues of the generic formula The epoxide addition reaction is convenientlycarried 0 0 out by adding the epoxide reactant gradually to the 'sec. onda 'lcam'e "m H2C/ OH -(OHt)n-0-- o ry g u 7 1n at such a te perature that the reaction proceeds without the further application of heat. Preand g y y ether y y ethers of aliph i a ferred temperatures are from about 80 C. to about 1501 aromatlc p y speclfic compounds falhng wlthln h c. The reaction may be carried out in the presence of several groups enumerated above are enumerated m to an inert diluent which may he a solvent for one or both tabular form below. of reactants Dihalides of aliphatic and araliphatic hydrocarbons: when the reacting functional-group is a halide, Q Ethylene di hl id action is one of condensation and the hydrohalide of the Ethylene dibromide condensed amine is formed. The free amine is obtained- 1,4-dichlor-butane p by treatment of the salt with an alkaline material. Alter 3 natively, and especially with halides, the free base may be'obtained directly by carrying out the condensation in the presence of a mild alkali such as sodium bicarbonate, calcium carbonate, or the like, to accept the formed hydrogen halide. A suitable solvent or diluent such as water, alcohol, lower ether alcohol, or the like, may be present and reaction temperatures of 90 to 150 C. are desirable. Superatmospheric pressures may be necessary to attain the desired temperature in the presence of water or other low boiling solvents.

After completion of the reaction, the sought product (the dihexityl amino compound) may be separated from the inorganic salts by known methods such as. ion-exchange, filtration, etc. The condensation reaction may be illustrated by the following equations showing the condensation of methyl glucamine with dichlorethylene.

Detailed preparations of several compounds in accordance with the invention is shown in the following examples.

EXAMPLE 1 Preparation of 1,3-di(N-methyl glucamin)- Z-hydroxy-propane A 3-liter, 3-neck flask fitted with a stirrer, thermometer, reflux condenser, and a dropping funnel was charged with 600 g. methyl glucamine and 300 cc. of water. The mixture was heated to 100 C. and the epichlorhydrin (141 g.) was added dropwise without the application of heat during 23 minutes, the heat of reaction being sutficient to maintain a temperature of 98100 C. A solution of 60 g. sodium hydroxide in 120 cc. water was added during nine minutes and the reaction mixture stirred at 100 C. for another hour after which the water was distilled off using vacuum (2.5 mm.) at the end to strip out all of the water at a final temp. of 140 C. The residue was dissolved in 800 cc. methanol and the solution filtered to remove inorganic salts. The methanol was then distilled otf, finally under vacuum leaving the di-glucamine as a resinous residue.

EXAMPLE 2 Preparation of 1,4 di(N-methyl glucamin0)-butane A l-liter, 3-neck flask fitted with a stirrer, thermometer and a reflux condenser was charged with 195 g. methyl glucamine, 64 g. 1,4-dichlorbutane, 300 cc. water and 84 g. sodium bicarbonate. The mixture was refluxed with stirring for about 17 hours after which the water was distilled off to a final temperature of 143 C. at 5 mm. The residue was dissolved in 250 cc. methanol and filtered to remove inorganic salts, after which the product (235 g.)

was recovered from the filtrate by distilling off the solvent. i

The product was resinous in nature "and containedsome inorganic salts.

7 EXAMPLE 3 g Condensation of N-methyl glucamine with a diepaxide in'tabular form below.

with the invention are presented 75 the less vigorously reactive Example N o 4 5 6 7 N -Me glucamine, 200 398 195 195.

gms. Dtfunctlonal Re- B O D O.

actant used. Dtfunctional Re- 102 188 71. 5 94.

actant, gms. Water, ml 180 300 2 300 300. Alkali used NaOH... NSaCOa--- NaHGOa NaHGOz. Alkali, gms 40 110 84 84. Reaction Time, hrs. 2. 5 9 14 13. 25. Reaction Temp., O 87-101- 110-125"" l00107 92-105. Alkali added after conafter conat start at start.

densate. densate.

1 B=3,3-dichlor-2,2-dihydroxy dipropyl ether; C=ethylene dibromide; D dichlordiethyl ether.

1 Oellosolve employed instead of water. 20 ml. water added after the N 3200.: was introduced.

The bis hexityl amine compounds of the invention are usually resinous in character, although their nature varies somewhat with their structure. The presence of higher alkyl radicals such as cetyl or stearyl, attached to the nitrogen of the glucamine residue renders the compounds waxy.

By virtue of the presence in the his hexityl amino compounds of reactive, or functional, groups, they can be readily converted into valuable functional derivatives which are useful as surface active agents, corrosion inhibitors, textile assistants, detergents, and the like. The said reactive groups are the hydroxyl radicals which may be readily esterified or etherified, and the tertiary nitrogen atoms which are susceptible to quaternization or to soap formation. Quaternization may be effected by reaction with alkyl or aryl halides or with inorganic acid esters of alcohols. Soaps of the his hexityl amino compounds are obtained by partial or complete neutralization of the tertiary nitrogen atoms with higher fatty acids, rosin or resin acids, tall oil, higher alkyl acid sulfates, higher alkyl aryl sulfonic acids and the like. Such functional derivatives are considered within the scope of the present invention.

Esters of the his hexityl amino compounds described herein may be prepared by direct esterification with organic acids, by reaction with acyl halides in the presence of alkalis, by reaction with acid anhydrides, by alcoholysis reaction with esters of organic acids, and the like. Acid radicals which may be introduced into the esters of the invention by one or more of the above methods include the radicals of acetic, butyric, caproic, capric, lauric, myristic, palmitic, stearic, oleic, behenic, linoleic, lactic, erucic, benzoic, p-tert. butyl benzoic, phenyl acetic, phenoxyacetic, 2,4-dichlorphenoxyacetic, 2,4,5-trichlorphenoxyacetic, rosin, tall oil, and other carboxylic acids.

When the esters are esters of the higher saturated fatty acids such as palmitic or stearic, they are hard Waxes. Unsaturated fatty acids yield softer esters. The higher fatty acid esters are conveniently prepared by bringing the his glucamino compound to a reaction temperature of.

to 220 C. and gradually introducing one or' more molecular proportions of the fatty acid thereto under vigorous agitation and in the presence of an inert atmosphere. When the first increments of acid are added, the viscosity of the reacting mixture is sharply increased, probably because of the formation of amine soaps of the fatty acids. 'At the reaction temperature, howeveryfithe soaps are soon decomposed and the fatty acids consumed by esterification, thereby restoring the higher fluidity of the reacting mass. "When all of the fatty acid is added,

the reaction is continued until the acid number reaches a substantially consistent low value. In the course'of the direct esterification ofthe his hexityl amino derivatives with higher fatty acids under the conditionsdescribed, some anhydridization .of.the polyhydric residues occurs, forming cyclic inner ether radicals. .This is evidenced by the evolution of more Water during the reaction than 1 can be accounted for by esterification. The ester products so obtained are mixtures of esters of his hexityl amino compounds and esters of partially anhydridized derivatives thereof. Examples 8 to 16 presented in tabular form below, show suitable reacting conditions for preparing specific fatty acid esters of his glucamino compounds within the scope of the invention.

Bis glucamino Fatty acid Reaction Conditions compound Ex. No.

used grams. used grams Time, Temp., Press.

Hrs. O.

8 Ex. 1 124 stearie 74. 4 150-190 1 to 2 mm 9-.- EX. 4 260 0leic 270 3% 164-218 atm. 10..-. Ex. 1.- 230 stear1c 149 1% 182-207 mm 11 Ex. 1-. 230 do 568 5% 190-212 atm. 12..-. Ex. 1.. 230 oleic 200 2% 183-196 6.5 to 22 mm 13..-. Ex. 1-. 109. 5 lauric.-. 46. 5 2% 190-194 atm. 14.". Ex. 2 215 stearic 197 2% 193-211 atm Ex. 6-. 217. 5 coconut- 177 334 186-213 atm 16.... Ex. 7 186 cottog- 250 4% 190-215 atm see The bis hexityl amino compounds of the invention, or their partial esters are readily susceptible to ether formation, particularly by reaction with alkylene oxides whereby hydroxy alkyl or hydroxy polyoxyalkylene ethers are formed. When the alkylene oxide is ethylene oxide the resulting hydroxyethyl ethers are more readily dispersible in water than are the starting compounds. 7

The hereinbefore described his hexityl amino compounds, their esters and/or their ethers may readily be converted to quaternary ammonium compounds by reaction with organic halides or inorganic acid esters of a1cohols. One or both of the tertiary nitrogen atoms of the compounds may be so converted to yield strongly basic compounds or salts of such strongly basic compounds. The said quaternary derivatives are of value as textile assistants, anti-static agents and as detergents.

What is claimed is:

l. A bis (N-alkyl hexityl amino) compound comprising two N-alkyl hexityl amino radicals linked by their respective nitrogen atoms through divalent radicals selected from the group consisting of alkylene, oxa-alkylene, hydroxy alkylene and hydroxy oxa-alkylene radicals.

2. Compounds as in claim 1 wherein the secondary hexityl amino radicals are N-methyl glucamino.

3. 1,3-bis(N-methy1 glucamino)-2-hydroxy-propane.

4. 1,2-bis(N-methyl glucamino)-ethane.

5. 2,2'-bis(N-methyl glucamino)-diethyl ether.

6. 3,3-bis(N-methyl glucarnino)-2,2 dihydroxy dipropyl ether.

7. The process of producing compounds containing two N-alkyl hexityl amino radicals which comprises reacting two molecular proportions of an N-alkyl hexityl amine with one molecular proportion of a compound containing two functional groups reactive with amino nitrogen selected from the group consisting of (l) alkylene and hydroxyalkylene dihalides, (2) oxa-alkylene and hydroxy oxa-alkylene dihalides, (3) alkylene and hydroxyalkylene diepoxides, (4) oxa-alkylene and hydroxy oxa-alkylene diepoxides, (5) halo-alkylene and halo-hydroxyalkylene epoxides, (6) halo-oxa-alkylene and halo (hydroxy)-oxaalkylene epoxides; wherein the said halide and halo-atoms are of atomic numbergreater than 10.

8. The process of claim 7 wherein the said difunctional compound is a dihalide.

9. The process of claim 7 wherein the said difunctional compound is a diepoxide.

10. The process of claim 7 wherein the said difunctional compound is a halo-alkylene epoxide.

11. The process of claim 7 wherein the saidhexityl amine is N-methyl glucarnine.

12. The process of preparing l,3-bis(N-methy1 glucamino)-2-hydroxy propane which comprises introducing gradually 1 molar proportion of epichlorhydrin into an aqueous solution of two molar proportions of N-methyl glucarnine at a temperature of about C., subsequently adding one molar proportion of aqueous alkali at the same temperature, and recovering the formed 1,3-bis(N- methyl glucamino) -2-hydroxy propane.

13. A composition comprising a carboxylic acid ester of the product of claim 1.

14. A composition as in claim 13 wherein the carboxylic acid is a higher fatty acid.

References Cited in the file of this patent UNITED STATES PATENTS 2,060,851 Calcott et al Nov. 17, 1936 2,091,105 Piggott Aug. 24, 1937 2,294,379 Bley Sept. 1, 1942 FOREIGN PATENTS 178,102 Sweden Sept. 2, 1935 

1. A BIS (N-ALKYL HEXITYL AMINO- COMPOUND COMPRISING TWO N-ALKYL HEXITYL AMINO RADICALS LINKED BY THEIR RESPECTIVE NITROGEN ATOMS THROUGH DIVALENT RADICALS SELECTED FROM THE GROUP CONSISTING OF ALKYLENE, OXA-ALKYLENE, HYDROXY ALKYLENE AND HYDROXY OXA-ALKYLENE RADICALS.
 7. THE PROCESS OF PRODUCING COMPOUNDS CONTAINING TWO N-ALKYL HEXITYL AMINO RADICALS WHICH COMPRISES REACTING TWO MOLECULAR PROPORTIONS OF AN N-ALKYL HEXITYL AMINE WITH ONE MOLECULAR PROPORTION OF A COMPOUND CONTAINING TWO FUNCTIONAL GROUPS REACTIVE WITH AMINO NITROGEN SELECTED FROM THE GROUP CONSISTING OF (1) ALKYLENE AND HYDROXYALKYLENE DIHALIDES, (2) OXA-ALKYLENE AND HYDROXY OXA-ALKYLENE DIHALIDES, (3) ALKYLENE AND HYDROXYALKYLENE DIEPOXIDES, (4) OXA-ALKYLENE AND HYDROXY OXA-ALKYLENE DIEPOXIDES, (5) HALO-ALKYLENE AND HALO-HYDROXYALKYLENE EPOXIDES, (6) HALO-OXA-ALKYLENE AND HALO (HYDROXY)-OXAALKYLENE EPOXIDES; WHEREIN THE SAID HALIDE AND HALO-ATOMS ARE OF ATOMIC NUMBER GREATER THAN
 10. 